低游离TDI聚氨酯固化剂的合成

采用催化聚合法合成了低游离TDI聚氨酯固化剂。讨论了催化剂用量，反应温度和反应时间对产品游离TDI含量的影响，中试和生产结果表明，采用该方法可以明显降低产品的游离TDI含量，并且对产品的其他性能没有明显影响。     

异氰酸酯TDI,MDI的合成技术与市场展望

本文介绍了合成聚氨脂所需的重要原料ＴＤＩ，ＭＤＩ的应用，生产工艺，特别谈到了非光气化法生产ＭＤＩ的合成新路线和ＴＤＩ，ＭＤＩ的国内外发展概况，并对市场现状进行分析，阐明了它广阔的发展前景。     

2005TDI——关税新变

05年开始，一些新的政策法规就要实施了。这些政策法规涉及到方方面面，包括我们的衣食住行，着实让我们感受到了新年的第一缕关怀。然而，作为一名PU人士，最关心的可能莫过于PU关税了。05年的TDI关税由暂定的4％升至6．5％值得人关注，这样的变化对PU业意味着什么?     

关于太化集团公司2万t／aTDI项目的思考与出路

依据试车中出现的问题，分析了问题的原因和教训，综合该产品市场、技术、体制与投资等方面，提出了走技术改造盘活存量的路子。     

TDI生产过程系统中焦油含量的测定

在参考国内外有关行业资料的基础上，结合TDI的生产实践，探索出TDI生产过程中焦油含量的热重测定方法，有较高的实用价值。     

价格

美国TDI供应商——陶氏、拜耳、利安德公司在上周对10月1日的合同价追涨10美分/磅（合220美元/吨，176欧元/吨），此次调价是针对美国本土TDI销售的价格调整。     

TDI生产TDA水分控制

本文对TDI生产所用主要原料TDA所含水分超标因素进行系统分析，制定相应对策，强化精细化管理，进行科学合理控制，实现水分含量符合指标要求，满足生产要求。     

热固性聚氨酯乳胶的研制

聚四氢呋喃醚二醇／甲苯二异氰酸酯为２（摩尔比）时，于约８０℃下反应３ｈ，生成聚氨酯（ＰＵ）预聚体，尔后滴加入丙酮／二乙撑三胺溶液中；再与环氧氯丙烷于５０℃下反应１ｈ，生成ＰＵ－脲－胺中间体，加３％乙酸水溶液，于５０℃下中和，在真空下脱除丙酮，即得外观呈半透明状热固性ＰＵ乳胶，其贮存期为０．５ａ。硫化条件１２０℃×２０ｍｉｎ下制得的胶膜具有好的力学性能。     

高真空两级分离聚氨酯固化剂中游离TDI的研究

采取高真空两级蒸馏分离聚氨酯固化剂中的游离TDI，在MD-S80内冷式薄膜蒸发器设备上通过调整真空度和温度，将游离TDI单体降低到0．28％以下，考察了影响分离的主要因素，达到用内冷式薄膜蒸发器分离TDI的目的。得到的TDI加成物和三级蒸馏相比，工艺简单，设备投资小，说明内冷式薄膜蒸发器设备采用两级分离聚氨酯预聚物中的TDI是可行的。     

低黏度二苯基甲烷二异氰酸酯型聚氨酯预聚体的合成

为了研究不同反应条件对聚氨酯预聚体(PPU)产品的黏度和贮存稳定性这两方面的影响,并探究获得低黏度、高储存稳定性的PPU的合成工艺,以二苯基甲烷二异氰酸酯(MDI)和聚丙二醇(PPG)为原料,考察了聚合温度以及加料方式对聚合反应和预聚体黏度的影响。结果表明,对于直接使用的预聚体,适当降低聚合温度和延长滴加时间有利于降低产品黏度;对于需要储存一段时间使用的预聚体,适当提高聚合温度和一次性加料有利于降低体系黏度,稳定性更好。     

氨纶技术进展

介绍了近年来国外利用氨纶原料二异氰酸酯、聚多元醇、扩链剂等改性氨纶的专利技术。包括采用具有空间位阻效应的二异氰酸酯提高耐黄变性和热定型效率 ,聚多元醇分子主链中引入类似紫外吸收剂的结构单元提高耐侯性和引入短支链结构二元醇提高耐水解性 ,低不饱和度聚丙二醇的应用以降低成本 ,短支链不对称结构扩链剂应用以提高热定型效率 ,采用多种添加剂和纺丝助剂等提高氨纶物性和可纺性。并对氨纶的技术发展方向进行了探讨     

Microphase-separated structure and mechanical properties of norbornane diisocyanate-based polyurethanes

Norbornane diisocyanate (NBDI: 2,5(2,6)-bis(isocyanatomethyl)bicyclo[2.2.1]heptane) is a new commercialized diisocyanate. NBDI-based polyurethane elastomers (PUEs) were prepared from poly(oxytetramethylene) glycol (PTMG), NBDI and 1,4-butanediol (BD) by a prepolymer method. Microphase-separated structure and mechanical properties of the NBDI-based PUEs were compared with general aliphatic and cycloaliphatic diisocyanate-based PUEs. The diisocyanates used were isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (HMDI) and 1,6-hexamethylene diisocyanate (HDI). Regular polyurethanes were also prepared as hard segment models from each isocyanate and BD to understand the feature of each hard segment chain. The HDI-based PUE showed the largest Young's modulus and tensile strength in the four PUEs due to the ability of crystallization of the hard segment component and the strongest microphase separation. HMDI has both properties of aliphatic and cycloaliphatic diisocyanates because of its high symmetrical chemical structure compared with NBDI and IPDI. On the other hand, the NBDI- and IPDI-based PUEs have an inclination to phase mixing, leading to decreased Young's modulus and tensile strength. The NBDI-based PUE exhibited better thermal properties at high temperatures due to stiff structure of NBDI.     

催化剂对HTPB-IPDI黏合剂体系的固化催化作用研究

为了降低黏合剂端羟基聚丁二烯( HTPB)和固化剂异佛尔酮二异氰酸酯(IPDI)的固化反应温度,提高生产效率,缩短固化时间,研究了二月桂酸二丁基锡(T-12)、乙酰丙酮铁(Fe(AA)3)和三苯基铋(TPB)3类催化剂对HTPB -IPDI黏合剂体系固化催化作用的影响.实验结果表明,加入TPB质量分数为0.05％时,其适用期可以达到6h,TPB是HTPB -IPDI黏合剂体系比较理想的固化催化剂.     

Rheo‐kinetic evaluation on the formation of urethane networks based on hydroxyl‐terminated polybutadiene

Rheo‐kinetic studies on bulk polymerization reaction between hydroxyl‐terminated polybutadiene (HTPB) and di‐isocyanates such as toluene‐di‐isocyanate (TDI), hexamethylene‐di‐isocyanate (HMDI), and isophorone‐di‐isocyanate (IPDI) were undertaken by following the buildup of viscosity of the reaction mixture during the cure reaction. Rheo‐kinetic plots were obtained by plotting ln (viscosity) vs. time. The cure reaction was found to proceed in two stages with TDI and IPDI, and in a single stage with HMDI. The rate constants for the two stages k₁ and k₂ were determined from the rheo‐kinetic plots. The rate constants in both the stages were found to increase with catalyst concentration and decrease with NCO/OH equivalent ratio (r‐value). The ratio between the rate constants, k₁/k₂ also increased with catalyst concentration and r‐value. The extent of cure reaction at the point of stage separation (x_i) increased with catalyst concentration and r‐value. Increase in temperature caused merger of stages. Arrhenus parameters for the uncatalyzed HTPB‐isocyanate reactions were evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1869–1876, 2001     

Preparation of Isophorone Diisocyanate Terminated Star Polyethers

Reactive star shaped isocyanate prepolymers have been prepared by endcapping hydroxy functionalized poly(alkylene oxide)s with isophorone diisocyanate. Selective reaction conditions have been worked out to reduce the amount of chain extension and crosslinking due to reaction of both isocyanate groups of the IPDI moieties. By combining ¹H and ¹³C NMR spectroscopy with size exclusion chromatography (SEC), the fractions of the monourethane isomers, and the extent of diurethane formation was determined. The effect of catalysis, of the excess of isocyanate, and of the type of poly(alkylene oxide) on the product structure and composition were investigated.     

Properties of segmented polyurethanes derived from different diisocyanates

Various segmented polyurethane materials with a polyurethane hard segment (HS) content of 40 wt % were prepared by bulk polymerization of a poly(tetramethylene ether) glycol with M_n of 2000, 1,4‐butanediol, and various diisocyanates. The diisocyanates used were pure 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (T100), toluene diisocyanate containing 80% 2,4‐isomer and 20% 2,6‐isomer (T80), isophorone diisocyanate (IPDI), hydrogenated 4,4′‐diphenylmethane diisocyanate (HMDI), and 1,6‐hexane diisocyanate (HDI). The segmented polyurethane materials were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), tensile properties, tear strength, and Shore A hardness. The DSC and DMA data show that the thermal transitions are influenced significantly by the diisocyanate structure. In the segmented polyurethane materials with aliphatic HS, the polyether soft segment (SS) is immiscible with the HS. However, in the segmented polyurethane materials with aromatic HS, the SS is partially miscible with the HS. The diisocyanate structure also influences the mechanical properties significantly and is described as the effect of symmetry and chemical structure of the HS. Various solution polymerized polyurethane resins with solid content of 30 wt % were also prepared and their thickness retention, water resistance, and yellowing resistance were determined for the evaluation of their usage as wet process polyurethane leather. The polyurethane resin with aliphatic HS show poorer thickness retention but better yellowing resistance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 167–174, 2000     

聚氨酯固化剂中TDI和HDI含量测试结果重复性差的原因分析

采用气相色谱仪和热重分析仪,对部分聚氨酯固化剂中的甲苯二异氰酸酯(TDI)和六亚甲基二异氰酸酯(HDI)含量测试结果重复性差的原因进行分析。结果得出结论 :主要是样品稳定性差的原因。     

异氰酸酯指数对木素型聚氨酯性能的影响研究

以羧丙基化木素和甲苯二异氰酸酯（TDI）或六亚甲基二异氰酸酯（HDI）为原料,采用溶液流延法制备了取氨酯,探讨了异氰酸酯类和用量对木素型聚氨酯的玻璃化温度,拉伸性能和在溶剂中溶胀性能的影响,结果表明,异氰酸酯指数（R值）和异氰酸酯类型对聚氨酯性能有大影响,随着R值的增加,TDI系列聚氨酯的玻璃化温度上升比HDI显著,HDI系列聚氨酯有二甲基甲胺中的溶胀各度随R值的增加而下降,R值的变化对拉伸强度影响不明显,HDI与羧丙基化木素制得的聚氨酯拉伸强度较TDI基聚氨酯的高,制备的木素型聚氨酯强度较高,有可能用作工程塑料。     

木素型聚氨酯的合成与性能研究

利用木素和两种二异氰酸酯合成了聚氨酯，对其热性能、力学性能、膨胀性能进行了测试。结果表明，羟丙基基化改性将木素变为聚酯－醚多元醇，可与二异氰酸酯合成木素聚氨酯；异氰酸酯基与羟基配比对用TDI与HDI合成的聚氨酯性能影响不同。